Nitrobenzeneazo-nu-difluoroalkyl-nu-hydroxyalkylaniline dye compounds



Patentecl Mar. 25, 1952 NI RQBEN ENEAZO- N -mFLUoRoALKY1;- N-HYDROXYALKYLANILINE DYE ooM- POUNDS Joseph B. Dickey, Rochester, N. Y assignor to Eastman Kodak Company, Rochester, N. Y a corporation of New Jersey No Drawing; ApplicationAugustfil 1949', Serial No. 109;056

'7 Claims; 1

Thls-invention'relates to new azocompounds containingv a difluoroalkylamino group andthelrapplication to the art of dyeing or coloringt'extile' matenemm-ade Of 61 containingiacellulose alli'yl c'airboxylic acid'e's't'er' having two to four carbon ato'm's iii the acid gfoups thereof.

It is known to' re a'rei azo dyes: containing a CB3 group: However;v so far as I am" aware in: every'instan'ce'the E3 group isdir'ectlyattachedf grouppre'sent 1n" the compound" of my" invention is" 1")' joined to a benzene nucleus" through an amino group rather than directly; (2) contains two rather than threefiuorine atoms and (3') hastWo" to five carbon atoms rather than a single carbon atom;

Ange'wandte Cheitni'e, v01. 52, page 457' (1939)" states that aminobenzotrifiuoride and its derive tlves when-diazotized and coupled with Naphthcl AS grounding componemsgive valuable color tones of exceptional light fastness. The combp nation" of one of these aminoloenzotri'fluoride basesw'ith' NaphtholAS is sai'dtob'ether e'd dye "used the" German flag.

The Ange'wan'dte' Chenli'e article refers to Ger manPatents 551',882 [U. S; 1,999,610], 588,781 [:U; S; 2,015,204]- and"590,255 to illustrate thedye compounds mentioned in thearticle'. These Ger man: patents disclose" cotton" ingrain azo: dyes prepared by coupling? diazotized" aminobenzotrifluoride compounds with 2,3 oxynaphthoic acid arylides' (Naphthol' AS- grounding. componets). Although efforts have been made to" apply Naphthol- AS type" dyes to cellulose" acetate textile-materials these dye compounds: have no utilityfor celluloseacetate textile materials. The dye compoundon Fa 0 CH3 Compound 2 of tabulation of German Patent 551,882

is typicalof the -compounds disclosed by the three German patents" above mentioned. Henne; in Gilman -Organic Chemistry-2nd ed;-- -page 963 (-1943) alludes to the light-fast trifluoromethyl lngrai'n: azodyes discussed in, the Angewandte Chemie article and states that the red dye used in the German flag bears a CF3 group on a naphthyl radical? Thatman'y azo compounds having a-CFa group are poor dyes forcellulose acetate textile: materials will be further apparent from the fact that the following azo compounds yield dyeings on" cellulose acetate t'extllematerials which have DoorfaJstrx'e'sdtdlight:

3 omomom I t & omcmo it NO; H3

cmcmon NOT- CHaCHzOH CHE CH} O H CHlCHzOH It will be understood that. the. foregoing. dye

compounds arev merely illustrative. of azo compounds containing a CR; group which yield dyeings on cellulose acetate textile materials having poor light fastness. There are many more such compounds.

After much investigation I have discovered that the azo compounds having the formula:

H SO NCzH group and Z represents a hydrogen atom, a bromine atom, a chlorine atom, a methyl group or an ethyl group, are valuable dyes for coloring textile'materials made of or containing a cellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof. They are particularly of use for the coloration of cellulose acetate textile materials. Depending upon their structure, they color the aforesaid textile materials orange, brownish-orange, scarlet, pinkish-red, red and rubine shades. The dyeings obtained in addition to having excellent fastness to gas possess unusually good fastness to light.

It is an object of my invention to provide new azo dye compounds. Another object is to provide a satisfactory process for the preparation of the new azo dye compounds of the invention. A further object is to provide dyed cellulose alkyl .carboxylic acid ester textile materials which possess very good fastness to light and gas. A particular object is to provide new azo compounds which are especially of value for the dyeing of cellulose acetate textile materials.

By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, I mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

The new azo dye compounds of my invention are prepared by diazotizing a primary aromatic amine having the formula: II. Y

N O NHz and coupling the diazonium compound obtained with a compound having the formula:

III. R

R1. X, Y and Z mthe'lsgejgqing formulas have the meaning previously assigned to them.

' ethylaniline, N 3,3 difluoro n propyl N- The aromatic amine compounds having the Formula II that are used in the preparation of the azo compounds of my invention are: p-nitroaniline, 4 nitro 2 chloroaniline, 4 nitro 2- bromoaniline, 4-nitro-2-fiuoroaniline, S-nitro- 2 aminophenylmethylsulfone, 4 nitro 2 trifiuoromethylaniline, 2 N methylsulfoneamicle- 4 nitroaniline, 2 N ethylsulfoneamide 4- nitroaniline, 4 nitro 2,6 dichloroaniline,

\ 4 nitro 2 chloro 6 bromoaniline, 4 nitro- 2 chloro 6 fluoroaniline, 4 nitro 2- methylsulfone 6 chloroaniline, 4 nitro 2- trifluoroznethyl 6 chloroaniline, 4 nitro- 2,6 dibromoaniline, 4 nitro 2 bromo 6- fluoroaniline, 4 nitro 2 methylsulfone 6- bromoaniline and 4 nitro 2 trifiuorornethyl- G-bromoaniline.

Typical of the coupling compounds (Formula III) that are used in the preparation of the azo compounds of my invention are: N-2,2-difiuoroethyl N B hydroxyethylaniline, N 2,2 difiuoro n propyl N 18 hydrcxyethylaniline, N 3,3 diflucro n propyl N B hydroxyethylaniline, N 3,3 difiuoro n butyl N l3- hydroxyethylaniline, N 2,2 difiuoroethyl N- ew dihydroxypropylaniline, N 2,2 difiuoron propyl N 5,7 dihydroxypropylaniline, N 3,3 difiuoro n propyl N 13, dihydroxypropylaniline, N 3,3 difiuoron propyle N firy dihydroxypropylaniline, N 2,2 clifluoroethyl N fa hydroxyethyl m chloroaniline, N 2,2 difluoro n propyl N B- nydroxyethyl m chloroaniline, N 3,3 diiluoro n propyl N 8 hydroxyethyl mchloroaniline, N 3,3 difiuorobutyl N 18- hydroxyethyl m chloroaniline, N 2,2 difiuoroethyl N 5, dihydroxypropyl mchloroaniline, N 2,2 diiluoro n propyl N- B, dihydroxypropyl m chloroaniline, N 3,3- difluoro n propyl N 5, dihydroxypropyl m chloroaniline, N 3,3 difiuoro nbutyl N 5, dihydroxypropyl m chloroaniline, N 2,2 difluoroethyl N ,8 hydroxyethyl m toluidine, N 2,2 difluoro npropyl N {3 hydroxyethyl m toluidine, N 3,3 difluoro n propyl N ,B hydroxyethyl m toluidine, N 3,3 difiuoro nbutyl N B hydroxyethyl m toluidine, N 2,2 difiuoroethyl N fi/Y dihydroxypropyl in toluidine, N 2,2 difluoro npropyl N {3, dihydroxypropyl m toluidine, N 3,3 clifiuoro n propyl N 5, dihydroxypropyl m toluidine, N 3,3 clifluoro n butyl N 5, dihydroxypropylm toluidine, N 4,4 difiuoro n amyl- N 5 hydroxyethylaniline, N 4,4 difiuoron amyl N B hydroxyethyl m chloroaniline, N 2,2 difiuoroethyl N {3 hydroxyethyl in bromoaniline, N 2,2 difluoroethyl N ,8 hydroxyethyl m ethylaniline, N 2,2 difluoroethyl N 7 hydroxypropylm bromcaniline, N 2,2 difluoro n propyl- N 8 hydrozyethyl m bromcaniline, N 2,2- difluoro n propyl N B hydroxyethyl m- ,8 hydroxyethyl m bromoaniline, N 3,"- difluoro n propyl N B hydrcxyethyl methylaniline, N 3,3 difiuoro n butyl N- p hydroxyethyl m bromoaniline, N 3,3- difluoro n butyl N 8 hydroxyethyl methylaniline, N 2,2 difluoroethyl N 3, dihydroxypropyl m bromoaniline and N 2,2- difluoroethyl N 5, dihydroxypropyl 'm'- ethylaninne. "an. .Ml ..:.'I.1'

good-c9 2 Itsl'ibuld" Beherenoted' that not all azo com-- pounds 'havinga 2,2-difluor'oeth'ylamino group, a"

coupling the coupling compounds of my invention with the diazonium form of 2,4-dinitro-6-chloroaniline, 2g4-dinitro-6-bromoaniline, 3,5-dinitro- 2-aminopheny1methylsulfone, 2,4-dinitro-6-tri fiuoromethyl-anilineand G-N-ethylSulforieamide- 2,4-dinitroani1ine yield dyeingson cellulose acetate:textilematerials which do not have goodfastness to -light. Similarly, the azo compounds prepared by diazotizing a compound having the Formula II and coupling the diazonium compound obtained with a:-oompo'und' having the formula;

I hydroxyalkyl wherein R1 represents a 2,2 difluoroethylgroup, a. 2.2-diiiuoro-n-propyl group. a 3,3difiuoronpropyl group, a 3,3-difluoro-n-buty1 group or a 4,4i-difiuoro-n-amyl group and Q represents a hydrogenatom or a methoxy group yield dyeings' on cellulose acetate textile materials which do not have good fa'stness to light.

Also, the azo compounds obtained by, diazotizing o-nitroaniline, 2-nitro-4-chloroaniline and 4-nitro-2-hydroxyaniline' and coupling the diazonium compounds obtained with the coupling compounds of the present invention yield dyeings oncellulose acetate textile materials which do not have good fastness tolight.-

While the azo compounds of my invention yield dyeings on cellulose acetate textile materials whichpossess unusually'good fastness to light and excellent fastness togas,- those compounds the, corresponding compounds wherein R is a 'yhydroxypropyl group or a dv-dihydroxypropyl group. From the foregoing, it logically follows thatlthosecompounds wherein-R and R1 are simultaneously a: 2,2-difiuoroethyl group and a fl hydroxyethyl group, respectively; are preferred.

Thefollowin'g examples illustrate the 9.20 compounds of my" invention and their manner of preparation."

EXAMPLE 1'- A. Preparation of m'trcsyl' sulfuric acid 7.6grams of dry sodium nitrate were added with stirring to 50 cc. of sulfuric acid (sp. gr. 1.8a) while keeping the temperature below 70 C. The resulting reaction mixture was then cooled to "C.-20 C'. andloograms of acetic acid were addddidpwis'e with stirring. following which the reaction mixture was cooled to 8'C.-10C.'

B. Didzotizlz'tidn' 21.6 grams of finely'powdered 5-nitro-2-am'ino phenyl-methylsulfone. were added slowly, with stirring, to the nitrosyl-sulfuric acid reactionmixture prepared as describedabove. The'reaction temperature was maintained below 20 C. After the' addition of the amine, grams of acetic acid were added dropwise with stirring. and the reaction mixture was stirred at'l5C.-20 C. until all of the amine had dissolved and the" diazotization reaction which takes place was complete: The diazon'ium solution was then poured onto 500 grams of crushed ice; and enough urea or sulfamic acid was added to destroy theexcess' nitrous] acid. The dia'zonium solution shouldbe' clearand free-ofsuspended undiazo'tized amine:

C Coupling iogramsof sulfuric-acid (Sp-gr. 1.84) were added to 20 co. of water and the resulting solu tion wascooled to 5 C. and then 20.1 grams-of- N 2,2 difiuoroethyl N- fihydroxyethylaniline were added while cooling. When solution was complete, 200 grams of crushed iceand 200 cc. of ice cold water were added to the reaction mixture. Then the diaz'onium solutionprepared, as described above, was added with stirring. Upon completion of the coupling reaction which takes place, sufficient sodium carbonate to' neutralize" the mineral acid present was slowly added to the reaction mixture. Sufiicient diazonium solution should be used to give a slight positive test (fora diazo solution) whenall the coupling component has reacted. The dye compound formed was recovered by filtration on a Buchner funnel,

washed free of salts with water and air dried. The yield of dye melting at C. C. was 40.6 grams. It has theform'ula:

and oolorscellulose acetate textile materials-scar let shades of excellent fastness to light and gasi In like manner by the use of 22.9 grams of l I-3,3-diiiuoro-nbutyl N B hydroxyethylaniline in place of N-2,2-difiuoroethyl-Nfi-hy droxyethylaniline, 43.3 grams of a dye melting at C.-l75 C. was obtained. It colors cel- CHQCHF:

cmcnion lulose acetate textile'materials ruioine shades of 4 excellent fastness to light and gas.

By contrast; the azo compound-of'theformulaz scion.

colors cellulose acetate textile materials yellow iSh crange shades which have poor fastnessto light. A

EXAMPLE 2 A. Diaeotization' 172 grams of 4-nitro-2-chloro'aniline were 10 grams of sulfuric acid (sp. gr. 1.84) were 5 added to cc. of water and the resulting solution was cooled to 5 C. and then 20.1 grams of N-2,2 difluoroethyl N ,8 hydroxyethylaniline were added while cooling. When solution was complete, 100 grams of crushed ice and 100 grams of ice cold water were added to the reaction mixture. Then the diazonium solution prepared as described above was added with stirring. Upon completition of the coupling reaction which takes place, sufilcient sodium carbonate to just neutralize the mineral acid present was added. Sufficient diazonium solution should be used to give a slight positive test (for a diazo solution) when all the coupling component has reacted. The dye compound formed was recovered by filtration on a Biichner funnel, washed free of salts with water and dried. The yield of dye meltin at 150 C.-15l C. was 37.4 grams. It has the formula:

CHQCHFZ onionion 20.7 grams of i-nitro--dichloroaniline were added portionwise, with stirring, to a nitrosyl sulfuric acid mixture prepared as described in Example 1 and simultaneously 10o grains of cold glacial acetic acid were added. The reaction mixture was stirred while keeping the temperature at about 15 C. until the diazotization reaction was complete. A clear, yellowish diazonium solution was obtained.

13. Coupling 20.1 grams of N-2,2-difluorcethyl-N-chydroxyethylaniline were dissolved in 800 cc. of 12 /2721 sulfuric acid. ilie resulting solution was cooled to 0 C.-10 C. by adding crushed ice with stirring. Then the diazonium solution prepared as descri ed above was added to the reaction mixture with stirring. Coupling takes place rapidly. The reaction mixture was cooled, with crushed ice, for example, as needed, to keep the reaction temperature at about 10 C.-15' C. The reaction mixture was stirred for about one-half hour after the addition of the diazonium solution and then slowly made neutral to Congo red paper with sodium bicarbonate after which it was allowed to stand for 1 hour. The dye compound formed was recovered by filtration, washed free of any salts with water and dried. The azo dye compound thus obtained has the formula:

l CHiCHF;

It colors cellulose acetate textile materials orange shades which have excellent fastness to light and gas.

By the use of 21.5 grams of N-2,2-difluoro-n propyl-N-o-hydroxyethylaniline in place of N- 2,2-difluoroethyl-N B hydroxyethylaniline, an azo dye compound is obtained which colors cellulose acetate textile materials orange shades which have excellent fastness to light and gas.

By way of contrast, the azo compound of the formula:

! cuicriion EXAMPLE 4 24.1 grams of i nitro 2 trifluoromethyl 6- chloroaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 20.1 grams or N-2,2-difluoroethyl-N-fi-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 3. I'he dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

By the use of 21.5 grams of N-2-,2-difiuoroethyl- N 'y hydroxypropylaniline and 24.5 grams or" N-2,2 difluoroethyl-N-cq-dihydroxypropylaniline, respectively, in place of N-2,2-difluoroethyl- N-p-hydroxyethylanilina dye compounds are obtained which similarly color cellulose acetate textile materials brownish-orange shades.

XANIPLE 5 28.5 grams of 4 nitro 2 triiluoromethyl-G- bromoaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 21.5 grams of I L-2,2-difluoroethyl-N-p-hydroxyethyl-m-toluidine. Coupling and recovery of the dye compound formed is carried out is accordance with the procedure described in Example 3. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

By the use of 20.1 grams of N-2,2difluoroethyl- N-,8-hydroxyethylaniline and 21.5 grams of l\l3,3 dii'iuoro n-propyl-N-p-hydroxyethylaniline, respectively, in place of N2,2-difiuoroethyl-N-chydroxyethyl-m-toluidine, dye compounds are obtained which color cellulose acetate textile materials brownish-orange shades.

EXAMPLE 6 21.6 grams of 5-nitro-2-aminophenylmethyl sulione are diazotizied in accordance with the procedure described in Example 1 and the diazonium compound obtained is coupled with 25.9 grams of N 3,3 difiuoro n butyl-N-e -dihydroxypropylaniline. Coupling and recovery of the dye compound formed'is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials rubine shades.

By the use of 24.3 grams or N-3,3-difluoro-nbutyl-N-v-hydroxypropylaniline and 23.1 grams of N 2,2 difiuoroethyl N --;s; -dihydroxypropylaniline, respectively, in place of N-3,3-difiuoro n butyl-N-on-dihydroxypropylaniline, dye compounds are obtained which color cellulose acetate textile materials rubine shades.

9 EXAMPLE ,7

"1733 grams of 4-nitro-2echloroaniline "are dia- Jzo'tized in accordance with the procedure "described in Example 2 and the diazonium com- "pound obtained is coupled with 243 grams of "N-lg i-difiuoro-n amyl-N B hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the proceduredescribed in Example 2. The dye compound obtained colors cellulose acetate textile "materials rubine shades which have excellent Ifastness to light and gas.

By the use of 13.8 grams of p-nitroailine in place of 4-nitro-2-chloroaniline, a dye compound :is obtained which colors cellulose :acetate textile materials orange shades which have very good fastness to light and gas.

By contrast, the azo compound of the formula:

J CHzCHzQHz'C FzCI-Ia I summon NQ: colors cellulose acetate textile materials rubine shades which have poorfastness to light.

EXAMPLE 8 016 grams of d- -nitro-2-trifluoromethylaniline are diazotized in accordance with the procedure describedingExample 2 and :the diazonium'compound obtained is coupled with '20.1grams of .N 2g2-difluoroethyleN p hydroxyethyla-niline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in 'Example2. The dye com- N7l /y-dihydroxypropylaniline and 28.7 grams of N-4,4 difluoro -.n -'amyl N-p,' -dihydroxypropylaniline, respectively, in place of N-2,2-di- 'l'luoroethyl-N-73-hydroxyethylaniline, dye comj'ipounds are obtained "which color cellulose aceitate ltextile materials red shades.

EXAMPLE 9 20.6 grams of 4.-nitro-2-trifluoromethylaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 24.9 grams of N- 3,3-difiuoro-n-propy1-N 8 hydroxyethyl m chloroaniliner Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The

dye compound.obtainedcolors cellulose acetate up textile materials red shades.

By the use of 29.4 grams of 'N-3,3-difiuoro-npropyl N )3 hydroxyethyl-m-bromoaniline in place of -l l -3,3-.difiuoro n-propyl-N-fi-hydroxyethyl-mchloroaniline, a dye compound is obtained which colors cellulose acetate textile ma- .terials red shades.

EXAMPLE 10 20;6 grams .of 4-nitro=2 trifluoromethylaniiine are diazotized'in accordance with the procedure described inExample ,2 and the diazonium compound obtained is coupled with 27.3 grams of N 2,2 difiuoroethyl-N-flw-dihydroxypropyl-methylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials rubine shades.

By the use of 25.9 grams of N-2,2-difluoroethyl N ,'Y dihydroxypropyl-m-toluidine in pound obtained colors cellulose acetate textile materials red shades.

place of N 2,2 .difluoroethyhN-B/y-dihydroxypropy1-.-m-,ethy1aniline, a dye compound is obtained which colors cellulose acetate textile materials rubine shades.

EXAMPLE 11 24.1 grams of 4-nitro 2-trifiuoromethyl-6- chloroaniline are diazotized in accordance with theprocedure described in Example '3 and the diazonium compound obtained is coupled with 21.5 grams of -N 2,2-difiuoro-n-propyl-N p hydroxyethylaniline. Coupling and recovery of the dyecompoundformed is carried out in accord- 'ance-with the'procedure described in Example3. The dye compound obtained colors cellulose ac- 'etate textile materials brownish-orange shades which' have excellent fastness to light and gas.

:By contrast, the azo compound of theformula:

'jCl /.CHzC-F:GHI N02- ,N=N+ N\ omcnlon .NOz

colors cellulose acetate textile materials rubine shades which have poor fastness to light.

EXAMPLE .13

20.7 grams of -4-nitro-2,6-dichloroaniline are 'diazotized in accordance with the procedure described in Example 3 and the diazonium-compound obtained is coupled with 24.9 grams of N 2,2 difiuoron propyl -"N )3 hydroxyethyl-m-chloroaniline. Coupling and recovery of the dye compoundformed is carried out in accordance with the procedure described in'Example The dye compound obtained colors cellulose acetate textile materials orange shades.

By the use of ?25;2 grams of 4-nitro-2-bromoo-chloroaniline in place of 4-nitro-2,6-dichloro- ;aniline,'a dyecompoundjisobtained which colors celluloseacetate textile materials ,orange shades.

EXAMPLE 114 .2037 grams of l-nitro 2,'6-dichloroaniline are vdiazotizedin accordance with the procedure described in Example ,3 and the diazonium .compound. obtained is coupled with 2613 :grams of N -.'3,3 -.difiuoro n -butyl N p -'hydr oxyethyl m-rchloroaniline. Coupling and recovery of .thedye compound 'formed'is carriedout 111130- cordance with the procedure described "in "Example '3. The dye compound obtained 'colors cellulose acetate textile materials orange'shades.

By the use of 28 grams of N-3,3-difiuoro-nbutyl N fl hydroxyethyl m bromoaniline :;and27.'7 gramsof N-4,4-difiuoroen-amyl-N-p-hy- :droxyethyl m --chloroan iline, respectively, in place of Ill-3,3edifluoro-nbutylaN-fi-:hydroxyll ethyl-m-cliloroaniline, dye compounds are obtained which color cellulose acetate textile materials orange shades.

EXAMPLE 15 19.2 grams of 4-nitr0-2 luoro-fi-chloroaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 20.1 grams of N 2,2 difluoroethyl N [3 hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 3. The dye compound obtained colors cellulose acetate textile materials orange shades.

By the use of 25.7 grams of N- igl-difluoro-namyl-N-'y-liydroxypropylaniline in place of N- 2,2-difluoroethyl-N--hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 16 13.8 grams of p-nitroaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 22.9 grams of N-3,3-difiuoro-nbutyl-N-,B-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials orange shades.

By the use of 22.9 grams of N-3,3-difluoro-npropyl-N-p-hydroxyethyl-m-toluidine in place of N 3,3 difluoro n butyl N ,8 hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades.

EXAMPLE 17 25.1 grams oi 4 nitro 2 methylsulfone 6- chloroaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 20.1 grams of N-2,2-difluoroethyl-N-c-hydroxyethylaniline. Coupling and recovery of the dye 1 compound formed is carried out in accordance with the procedure described in Example 3. The dye compound obtained colors cellulose acetate textile materials orange shades.

By the use of 21.5 grams of N-2,2-difiuoro-npropyl-N-B-hydroxyethylaniline in place of N- 2,2-difluoroethyl-N-B-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAIVIPLE 18 ethyl-N- 8-hydroxyethyl-m-toluidine in place of N-3,3-difiuoro-n-propyl-N-c,vdihydroxypropylaniline, a dye compound is obtained which colors cellulose acetate textile materials orange shades.

EXAMPLE 19 24.5 grams of 2-N-ethylsulfonamide-4.-nitroaniline are diazotized in accordance with the procedure described in Example 1 and the diazonium compound obtained is coupled with 20.1 grams of N-2,2-difiuoroethyl-N-[i-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials red shades which have very good fastness to light.

By the use of 27.3 grams of N-3,3-difiuoro-nbutyl-N-c, -dihydroxypropylaniline in place of N2,2-difluoroethyl N-[i-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades which have very good fastness to light.

By contrast, the ass compound of the formula:

CHQCHOHCHiOH colors cellulose acetate textile materials reddishviolet shades which have poor fastness to light.

EXANiPLE 29 23.1 grams of 2-N-methylsulfonamide-d-nitroaniline are diazotized in accordance with the procedure described in Example 1 and the diazonium compound obtained is coupled with 20.1 grams of N-2,2-difiuoroethyl-l T-,B-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials red shades.

By the use of 22.9 grams of N-SB-difluoro-nbutyl-N-{3-hydroxyethylaniline in place of N-2,2- difiuoroethyl-N-;8-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades.

Following the procedure described in Examples 1 to 20, inclusive, the dye compounds indicated hereinafter were prepared. The color is that which the dyes give on cellulose acetate textile materials.

Dia'm Component Coupling Component Color 5 mil-r0 aminophcnyl N3,3-difluoro-nbutyl-Nfi- Rublne.

hydroxyethyl-m-toluidinc. N -2,2 difluorocthyl N 8 Do. hydroxyethyl-in-toluidinc. 4 N 2,2 difluoroethyl -N 7 Rev hydroxypropylaniline. N- 3-difiuoro-n-butyl-N-fl- Do.

hydroxycthylanilino. N-3,S-diiluoro-n-butyl-N-fi, Do.

v-dihydroxypropylanilinc. N -2,2 difllloroethyl N 5 Do.

hydroxycthyl m chloro aniline. N 2,2 difiuorocthyl N 5 Ruhine.

hydroxycthyl-m-toluidiuc. N-2,2-difiuoroethy1-N- 5.7 Do.

dihydroxypropyl-m-tolnidine. 4 uitro 2 trifluoi'o N-2,2-(lifluorocthyl-N-B- BrownishmothvLG-chloronniiinc. hydroxvethyl-m-toluidino. Orange.

Do N-22 .1oroethyl-N-fiby ycthyl m chloro aniline. 4-11itro-2-trifluorometh- N-2,2-difluoro-n-propyl-N- Do.

yl-fi-ohlorocniline. droxyethyl-lnchloroaniline. v Do N-2,2-difluoro-n-propyl-N- l Do.

y-hydroxypropylaniline. lmitroanilinc N -2,2-(liii'.1oroeth,v1-N-B- Ormm hydroxyethylaniliuc. 4:nitro-2,6dichlorooni- N-3,3-difluoro-u-butyl-N-,8- Do.

line. hydroxyothyl' uiline.

Do N- iA-difluoro-n amyl-N-flo. hydroxyethyhnilinc. 5-nitro-2-aminopheuy1- N-4, i-difluoro-n-amyl-N-(3- Rubmc.

methylsulfonc. hydroxycthylaniline.

Do N-i,4-difiuoro-n-amyl-N-B- Do.

hydroxyethyl-m-toluidino.

While not-all oi the compounds ofmy'invention liavebeen specifically described, the manner ofpreparingany of the compounds is believed tobe'obvio'u's from the numerous examples given hereinbefore;

Dye compounds corresponding to those described hereinbefore but which contain at least oi1e-OSOsH group or this-group in its salt form have also been prepared. These dye compounds containing a'sul-fato group are prepared either by introducing a sulfa-to group into the dye com p'oundspreviously described or by introducing a sulfate group into the coupling components of the present invention and coupling the compounds thus obtained with the diazonium compounds used in the preparation of the new azo compounds of the invention. These new dye compounds are suitable for dyeing the textile materials men' tioned hereinbefore as well as silk, wool and ny- Ion textile materials. Because of the increased Water solubility oi these new dye compounds, they are particularly adapted for dyeing cones of yarn and fabrics of close weave and of heavy construction.

The following examples illustrate the manner in which these new sulfato dye compounds are prepared.

EXAMPLE'ZI 4237 grams of omcmon scion;

CH OHF';

salt form of the dye is desired, the evaporation step is omitted. Instead, following the addition of the-300 cc. of ice and water, the reaction mixture is neutralized with sodium hydroxide (other suitable organic or inorganic bases can be used) warmed to dissolve the dye, filtered to remove any insoluble material and then concentrated under reduced pressure until the dye separates. The dye compound thus obtained has the formula:

oinonr,

S O2CH It'colors cellulose acetate, wool, nylon and silk textile materials red shades from an aqueous so- CH2CHzOSO Na luti'on or suspension.

EXAMPLE 22 hours. Following this thereaction mixture is cooled andthe pyridine is removed underreduced pressure. 30000; of ice and' waterare then added to the reaction mixture" and the dye-*is recovered by evaporation; The dye compound obtained colors cellulose acetate textile materials scarlet" shades;

EXAMPLE 23 41.7 grams of 4-nitro-2,6-dichlorobenzeneazo- N-2,2-difluoroethyl Nfl-hydioxyethylaniline are mixed with 50" cc. of sulfuric acid (sp. gr. 1.84) and the reaction mixture resulting iswarmed to 50C; for 3 hours and' then cooled to 0* C. 200 cc. of ice and water'are added and the reaction mixture is made neutral to Congo redpaperwith sodium bicarbonate. Thedye compound formed is recovered by filtration and Washed with cold salt water. The dye compound thusobtained colors collulo'se acetate; silk, wool and nylon orange shades.

EXAMPLE .24

20.6 grams of 4-nitro-2=trifluoromethylaniline are diazotized inaccordance with the procedure described in Example 2 and the diazonium compound obtained'is coupled with 42.7 grams of the sodium salt of N-2,2 difiuoro-n-propyl-N-B-sulfatoethylaniline. Coupling and recovery of the dye compound formed iscarried out in accordance with. the procedure described in Examp1e2. The dye compound obtained colors cellulose acetate, wool. silk and nylon red shades.

From the foregoing examples the manner of introducing a sulfa-to groupinto any of the use compounds of my inventionis'belie'ved to be clear, especially since the manner of introducing a sulfato group is known to those skilled'in the am Any-"other suitable way of introducing the sulfate group into the dye molecule can be employed. The sulfate group c'an'bepresent in its free acid form or in the form of'an inorganic'or organic base salt such as, ior example, the Na, K, Nl 'ii, Mg, ca, Li, me'thyl'amine, di'rnethylamine, trimethylamine, pyridine, aniline, guanidine, semicarbazide; biguani'dine; phenyl guanidine', cycl'ohexylam'ina' dicyclohexylamine, tetrahydrofurfuryla'mine'o1 alkanolamin'e salt form.

In order that the preparationofthe az'o compounds of my invention may; be clearly understood, the preparation of certain intermediates used in their manufacture is describedhereinafter.

990 grams of concentrated hydrochloric acid and- 500 grams of glacial acetic acid were'placed in a 2-liter flask equipped with a-chlorine inlet tube; a gas escape tube attached toawater trap, a mechanical stirrer, a thermometer and a cooling bath. Then 206 grams of finely powdered 4-nitro-2-trifluoromethylaniline were added" to the mixed acids. The reaction mixture was cooled to 10 C. and about '73 grams of chlorine were gradually introduced with. vigorous stirring. over a period of 4 to 6 hours while keeping the temperature between 10 (Bl-15 C. The reaction proceeded rapidly without much evolution of heat and 4 nitro 2 trifiuoromethyl' 6 chloroaniline separated as a fine yellow solid. Toward the end of the chlorination, the rate of addition' of chlorine was materially lowered to avoid decomposition of the 4-nitro-2 trifluoromethyl- 6-chloroan'iline.

the reaction mixture denser.

. wise with stirring.

. a stirrer and a thermometer.

When about 73 grams of chlorine (or until a sample gives the desired melting point) had been absorbed, the chlorine addition was stopped and stirred for one hour to complete the reaction. The reaction mixture was then filtered on a Biichner funnel to recover the precipitated 4 nitro 2 trifluoromethyl- S-chloroaniline. The filter cake was washed with 100 grams of acetic acid and then with 175 grams of Water.

After drying, the compound melted at 112 C." 114 C. and after crystallization from acetic acid it melted at 115 C.-116 C. The yield of e-nitro-2-trifluoromethyl-G-chloroaniline was 228 grams which is 95% of the theoretical.

iErcampZe B.--4-nitro-2-irifluoromethyl-d-bromoaniline 29.6 grams of l-nitro-.Z-trifluoromethylaniline were dissolved in 106 cc. of acetic acid and 16.8 grams of bromine in 100 cc. acetic acid were gradually added at 40 C. The reaction mixture was placed on a steam bath for 4 hours under a con- Then it was cooled and poured into ice water. i-nitro'2-trifluoromethyl-6-bromoaniline precipitated as a yellow solid and was recovered by filtration. The filter cake was washed with a water solution of NaHSOa. then with water and dried. It melted at 140 C.-l .l2 C. The yield was 26 grams.

Example C .-4-ntro-2-methg lsul fone-5-chloroaniline 50 grams of 5-nitro-2-aminophenylmethy1sul- The perature at about C.- C. Chlorine was bubbled: in for about 4 to 5 hours and then the reaction mixture was drowned in cold water. 4-nitro-2-methylsulfone-6-chloroaniline precipitated and was recovered by filtration. It was washed with cold water, then with a saturated solution of NaHSOa and finally with water. Upon drying and recrystallization from glacial acetic acid the product melted at 224 C.-225.5 C. Before recrystillization it melted at 2li C.-216 C.

The yield was 4'7 grams.

Ex mple D.4-niiro-2-methylsulfovze-6dimmc aniline 21.6 grams of 5-nitro-2arninophenylmethylsulfone were placed in 200 cc. of glacial acetic acid and 16.5 grams of bromine were added drop- After about 6 hours the reaction mixture was warmed on a steam bath under a condenser. After minutes the reaction mixture was cooled, poured into water and liltered. .l-nitro-2-rnethylsulfone-G-bromoaniline was obtained as yellowish crystals which were washed with aqueous NazCOs and dried. II desired, a purer product can be obtained by crys- .tallization from hot acetic acid.

Example E.-4-nitro 2-chZoro-6-fiuoroaniiine 90 grams of concentrated hydrochloric acid (sp. gr. 1.14), grams of glacial acetic acid and 15.6 grams of 4-nitro-2-fluoroaniline were placed in a 3-necked 500 cc. round-bottomed flask, fitted with The reaction mixture resulting was cooled to 10 C.-15 C. and chlorine was slowly introduced to the stirred reaction mixture at 10 C.-15 C. until 7.5 grams had been taken up. This usually takes 24 hours. Stirring was continued for an additional hour and If desired, the chlorination can be carried out in a dilute sulfuric acid medium.

Eramplc F.-4-m'tro2-bromo6-fiuoroaniline This compound is obtained by the use of bromine in place of chlorine in Example E. It is a yellow crystalline solid.

Compounds having the formula:

Iv. onic-men are prepared by reacting ethylene oxide with a compound having the formula:

1 R1 2 R1 and Z in the foregoing formulas have the meaning previously assigned to them.

The following examples are illustrative of the manner in which the compounds of the Formula numbered IV are prepared.

7.9 grams of N-2,2-difluoro'upropylaniline. 1.9 grams of ethylene oxide and 10 cc. of ethyl alcohol were heated with shaking in a sealed tube for 8 hours at 185 C. The contents of the tube were cooled, removed from the tube and distilled reduced pressure. About 3 grams of N-2,2 difluoro-n-propyl-N-c-hydroxy-ethylaniline boiling at C.-l69 C./l1 mm. were obtains:

Example I .--N2,2-difluoro-1ipropyZ-N- chyd'roscyethyl-m-chlorodniline 7.6 grams of N 2,2 difiuoro-mpropyl-mchloroaniline,'l.9 grams of ethylene oxide and 5 c. of ethy. alcohol were heated with shaking in a ealed tube for 15 hours at 200 C. Then the contents or the tube were cooled, removed from the tube and distilled under reduced pressure. 3 grams of l\l-2,2-difiuoro-n-propyl W-c-hydroxyethyl-m-chloroaniline boiling at C.l'?0 C./6 min. were obtained.

Example J.-N3,3-dijZu.oro-uJmtyZ-N-chydroxyethylrmiline 16.4. grams of N--3,3difluoron-butylaniline and grams of ethylene oxide dissolved in 10 cc. of ethyl alcohol were heated in a sealed tube at 180 C. for 24 hours. The resulting reaction sure in a small helix-packed column. N-3,3- difluoro-n-butyl-N- 3-hydroxyethylaniline, boiling point 140 C.-143 C./1.5 mm., n 1.5142, was obtained in 84% yield.

Example K.-N-4,4-diflaoro-n-amyZ-N-fihydroxyethylaniline 10 gram of N4,4-diiluoro-n-amylaniline, 2.6 grams of ethylene oxide and 10 cc. of ethyl alcohol were heated, with shaking, in a sealed tube at 200 C. for 15 hours. The reaction mixture was cooled, removed from the tube and distilled under reduced pressure. 10 grams of N-4,4- difiuoro-n-amyl-N-B-hydroxyethylaniline boiling at 170 C.172 C./7 mm. were obtained.

In a manner similar to that described in Examples G, H, I, J and K, N-2,2-difluoroethyl-N fl-hydroxyethyl-m-choroaniline, B. P. 180 C.- 182 C./14- mm. N 2,2 difluoroethyl N-fi-hydroxyethyl-m-toluidine, B. P. 120 C./2 mm.; N- 3,3 difluoro n butyl N c-hydroxyethyl-mtol-uidine, B. P. 135 C./1 mm., 12 1.5165; N-3,3- difluoro-n-butyl N B-hydroxyethyl-m-chloroaniline, B. P. 162 C./1.5 mm., n 1.5300; N-2,2- difluoroethyl-N-B-hydroxyethyl-m-toluidinc, B. P. 155 C.-158 C./7 mm.; N-2,2-difluoro-npropyl-N-,3-hydroxyethyl-m-ethylaniline, B. P. 130 C.132 C./1 mm.; N -4,4-difluoron-amyl-N- fl-hydroxyethyl-m-chloroaniline, B. P. 165 C.- 168 C./1 mm.; N-3,3-difiuoro-n-propy1-N-flhydroxyethylaniline, B. P. 135 C.-136 C./2 mm.; N 4 3,3 difiuoro-n-propyl-N-/i-hydroxyethyl-mtoluidine, B. P. 130 C./l mm.; N-3,3-difluoro-npropyl-N-fi-hydroxyethyl -m ethylaniline, B. P. 131 C.-132 C./1 mm.; N-2,2-difiuoroethyl-N/3- y-dihydroxypropylaniline, M. P. 46 C.53 C.; N-2,2 difiuoro-n-propyl N-B-hydroxyethyl-methylaniline, B. P. 131 C.-132 C./l mm.; etc., are prepared.

Compounds having the formula:

VI. CHzCHzCHzOH wherein R1 and Z have the meaning previously assigned to them are prepared by reacting trlmethylene chlorohydrin or trimethylene bromohydrin with a compound having the Formula-V.-

The following examples are illustrative of the manner in which the compounds having the Formula numbered VI are prepared.

L.N-3,3-difluro-n-propyZ-N-' hydroxypropylaniline Example M .-N -.2,2-difluoroethyl-N hydroxypropyl-m-toluidine 51.3 grams of N-2,2-difiuoroethyl-m-toluidine were reacted with 30 grams of trimethylene chlorohydrin in accordance with the procedure described in Example L. N-2,2-difluoroethyl-N- Example 18 -hydroxypropyl-m-toluidine boiling" at 134 0.- 138 C./2 mm. was obtained.

Example N.N-2,2-difZuoro-n-propyl-Nwhydroxypropylaniline.

51.3 grams of N-2,2-difluoro-n-propylaniline, 46.4 grams of trimethylenebromohydrin and 30.5 rams of NaHCOz were heated at 140 C. for 6 hours with stirring. Upon cooling benzene was added to the reaction mixture and the reaction mixture was filtered. The benzene was removed from the filtrate and the portion remaining was distilled under reduced pressure to obtain N -2 ,2 difl-uoro n propyl N-v-hydroxypropylaniline boiling at 137 C.-140 C./1 mm.

Following the procedure described in Examples L, M and N, N2,2-difluoro-n-propyl-N-y-hydroxypropyl-m-chloroaniline, N-2,2-difiuoro-npropyl-N-v-hydroxypropyl-m-toluidine, N 3,3- difiuoro-n-propyl-N-y-hydroxyproml m toluidine, N-3,3-difiuoro-n-butyl-N-y-hydroxypropylm-toluidine boiling at 183 C.-186 C./6 mm., N 3,3 difluoro-n-butyl-N-y-hydroxypropyl-mchloroaniline boiling at 190 C.-195 C./6 mm.; N-2,2 difiuoroethyl-N-v-hydroxypropy1 aniline boiling at 117 C.-l21 C./12 mm., and N-3,3- difiuoro-n-butyl-N-- -hydroxypropylaniline boiling at 178 C.l C./6 mm. are obtained.

grams of N-4,4-difluoro-n-amy1aniline and 30 grams of trimethylene chlorohydrin were heated together on a steam bath for 10 hours. The reaction mixture was 'cooled and made just basic by adding 10% aqueous NaOH. Benzene was added to the reaction mixture and the reaction mixture was filtered. The filtrate was washed with water and the benzene portion was distilled under reduced pressure. N -4,4-difluoron-amyl-Nw-hydroxypropylaniline boiling at 180 C.- C./7 mm. was obtained. It is a heavy colorless liquid.

Similarly N -4,4-difluoro-n-amyl 7 hydroxypropyl m chloroaniline and N-4,4difiuoro-namyl-y-hydroxypropyl-m-ethylaniline, B. P. 185 C.189 C./6 mm., for example, are obtained.

Compounds having the formula:

VII. CHzOHOHCHzOH wherein R1 and Z have the meaning previously assigned to them are prepared by reacting glycerol chlorohydrin with a compound having the Formula V. p

The following examples are illustrative of the manner in which the compounds of the Formula numbered VII are prepared.

Example P.-N-2,2-difluoro-n-propyl-N-d'ydz'hydromypropylaniline 17 grams'of N-2,2-difluoro-n-propylaniline, 10 grams of NaI-ICOs, 100 cc. of amyl alcohol and 12 grams of glyceryl chlorohydrin were heated distillation under reduced pressure and then the reaction mixture was steam-distilled under reduced pressure to remove any unchanged N-2,2-

difluoro-n-propylaniline. Following this the reac- 19 tion mixture was extracted with benzene and the benzene extract was distilled to dryness under reduced pressure. N2,2-difluoro-n-propyl-N- Bry-dihydroxypropylaniline was obtained. It is a straw colored, viscous compound.

Example Q.N-3,3-dijluor-n-butyZ-N-5 dihydroatypropylaniline 9 grams of N-3,3-difluoro-n-butylaniline and 4.6 grams of NaHCOa were stirred and heated together at 145 C. by means of an oil bath while 6.1 grams of glyceryl chlorohydrin were slowly added. After the addition, heating and stirring at 145 C. were continued for 6 hours. The evolution of carbon dioxide ceased after an hour. An equal volume of water was then added to the reaction mixture and the reaction mixture was extracted three times with benzene. The benzene solution was steam-distilled, leaving the reaction product as an oily residue. The yield of crude N-3,3-difiuoro-n-butyl-N- 5,7 dihydroxypropylaniline was 95%. Upon distilling the crude product in a molecular still (i. e. a Hickman molecular still manufactured by Distillation Products, Inc., Rochester, N. Y.) under a reduced pressure of 22 microns at 110 C.- -125 C., N3,3-difluoro-nbutyl-N-5,y-dihydroxypropylaniline was obtained as a clear, ver'y viscous oil N 1.5230.

12 grams of N-3,3-difluoro-n-butyl-m-toluidine, 5.6 grams of NaHCO: and 7.3 grams of glyceryl chlorohydrin were heated together at 145 C. for '7 hours in accordance with the procedure described in Example P. The crude reaction product thus obtained was distilled in a molecular still (i. e. a Hickman molecular still manufactured by Distillation Products, Inc., Rochester, N. Y.) under a reduced pressure of 11-14 microns at a temperature of 110 C. N-3,3-difluoro-n-butyl-N- 5, -diyhydroxypropyl-m-toluidine was obtained. Upon recrystallization from hexane it melted at 81 C.

Example S.-N-2,2-difluoroethyl N B/v dihydroxypropyl-m-toluidine This compound was obtained byreacting 10.3 grams of N-2,2-difiuoroethyl-m-toluidine, 5.6 grams of NaHCOs and 7.3 grams of glyceryl chlorohydrin together in accordance with the procedure described in Example Q.

Example T .N -4,4-difluoro n-amyl-N -flfY-dihydroxypa-opylaniline '20 grams of N-4,4-difiuoro-n-amylaniline, 10 grams of NaHCOs, 100 cc. of amyl alcohol and 12 grams of glyceryl chlorohydrin are heated together under refluxing conditions for 6-10 hours. Then 2 grams of charcoal are added and the reaction mixture is stirred and filtered to remove the charcoal, salt'and any other insoluble material. Upon working up the reaction mixture in accordance with the procedure described in Example P, N-4,4-difluoro-n-amyl N fi/Y dihydroxypropylaniline is obtained. It is a strawcolored, very viscous-compound.

Following the procedure described in Examples P, Q, R, S and T, N-2,2-difiuoro-n-propyl-N- flfy-dihydroxypropyl-m-chloroaniline, N-2,2 difluOrO-n-propyl-N-,B,'y-dihydr0xypropyl-m toluidine, N-3,3-difluoro-n-propyl-N-fi -dihydroxypropylaniline, N-2,2-difiuoroethyl-N 18, dihydroxypropylaniline, N-3,3-difluoro-n-propyl N- Bn'-dihydroxypropyl-m-chloroaniline, N-3,3 di- 20 fiuoro-n-butyl-N-fi,'y-dihydroxypropyl-m-chloroaniline, N-4,4-difiuoro-n-amyl-N-fi,'y-dihydroxypropyl-m-toluidine, N-2,2-difiuoroethyl N findihydroxypropyl-m-ethylaniline; etc. are prepared.

Compounds having the formula numbered V are prepared by reacting a compound having the formula VIII.

with 1,1-difiuoro-2-bromoethane or 1,1-diflu0ro- 2-chlor0ethane, 3,3 difiuoro n propylbromide (CHFzCHzCHzBr) 2,2-difluoro-n-propylbromide (CHsCFzCHzBr) 3,3 difluoro n butylchloride (CHsCFzCHzCHzCl) and 4,4 difiuoro n amylchloride (CHaCFzCHzCHzCHzCl), respectively.

The following examples are illustrative of the manner in which the compounds of the formula numbered V are prepared.

Example U.--N-2,Z-difluoroethylaniline 72.5 grams of 1,1-difluoro-2-bromoethane, 46.5 grams of aniline, 42 grams of sodium bicarbonate and 1 gram of sodium iodide were heated together with shaking in an autoclave for 15 hours at 150 C. After cooling to room temperature, the reaction mixture was removed from the autoclave by washing with benzene (200 grams) and water and filtered to remove a small amount of insoluble material. The benzene layer was washed with water and then the benzene was removed by distillation. Upon distillation under reduced pressure through a 12" indented column, 66 grams of N-2,2-difluoroethylaniline, boiling at 104 C.-106 C./ 19 mm. was obtained.

Example V.-N-2,2-difluoro-n-propylaniline 28 grams of aniline, 43 grams of 2,2-difiuoro-npropyl-bromide, 25 grams of sodium bicarbonate and 1 gram of sodium iodide were placed in an autoclave and heated 24 hours at 170 C, with shaking. The reaction mixture was then cooled, washed out of the autoclave with benzene and filtered. The benzene was then removed from the filtrate and the residue containing the desired reaction product was distilled under reduced pressure. A good yield of N-2,2-difiuoro-npropylaniline boiling at 103 C.-107 C./12 mm. was obtained.

Example W.-N-3,3-difluoro-n-propylaniline By the use of 43 grams of 3,3-difluoro-npropylbromide in place of 2,2-difluoro-n-propylbromide in Example W, N-3,3-difluoro-n-propylaniline boiling at 125 C.-126 C./ 16 mm. was obtained.

Following the procedure described in Examples U, V and W, N-2,2-difluoroethyl-m-toluidine, B. P. 140 C.141 C./27 mm.; N-2,2-difiuoroethyl-m-chloroaniline, B. P. 129 C.133 C./l6 mm.; N-2,2-difluoro-n-propyl-m-toluidine, B. P. C.-117 C./l2 mm.; N-2,2-difluoro-n-propylm-ethylaniline, B. P. 120 C.-123 C./12 mm.; N-2,2-difluoro-n-propyl m chloroaniline, B. P. 115 C.-120 C./'7 mm.; N-2,2-difluoro-n-propylm-bromoaniline, B. P. 125 C.-128 C./7 mm.; N-3,3-difiuoro-n-propyl m toluidine, B. P. 146 C.-147 C./27 mm.; N-3,3-difluoro-n-propyl-mchloroaniline, B. P. 110 C.-114 C./4 mm.; N-2,2-difiuoroethyl-m-ethylaniline, B. P. 103 C.- 108 C./7 mm.; etc, are prepared.

Example X.-N-3,3-difluoro -n-butylanili ne A mixture of 24 grams of 3,3-difiuoro-n-butylchloride (CH3CF2CH2CH2C1) and 35.3 grams of aniline were heated in a sealed tube at 160 C. for 24 hours. Upon cooling, the tube was opened and the oily solid content was washed out with a aqueous sodium hydroxide solution, yielding an oil. The aqueous phase of the reaction mixture was extracted with ether, and the ether extract was combined with the oil. After drying the ether solution over K2003, the ether was removed, and the residue was fractionated under reduced pressure in a small helix-packed column. A 54% yield of N-3,3-difiuoro-n-butylaniline boiling at 122 C.-123 C./10 mm. 12 1.5087, was obtained.

In like manner, N-3,3-difluoro-n-butyl-m-toluidine boiling at 135 C.136 C./10 mm. 12 1.5054 N-3,3-difiuoro-n-butyl m chloroaniline boiling at 149 C.-151 C./8 mm., n 1.5330, for example, are obtained.

Example Y 28.5 grams of 4,4-difluoro-n-amylchloride and 37 grams of aniline are heated together in an Erlenmeyer flask on a steam bath for 36 hours. The reaction mixture is cooled and made alkaline by the addition of 10% aqueous NaOH. Then the reaction mixture is extracted with benzene and the benzene extract is distilled under reduced pressure. N-4,4-difluoro-n-amylaniline boiling at 101 C.102 C./2 mm. is obtained.

Following the procedure described in Example Y, N-4,4-difiuoro-n-amyl-m-toluidin-e, B. P. 153 C.-155 C./11 mm.; N-4,4-difluoro-n-amyl mchloroaniline, B. P. 152 (Lt-154 C./8 mm.;"etc. were prepared.

1,1-difluoro-3-bromopropane (CHFzCHzCHzBr) appears to be a, new compound. It was prepared as described hereinafter.

Example Z.-Prep=aration of 1.,1-difluoro- 3-bromopropan 98 grams of 1,1,3,-tribromopropane were placed in a 200 cc. round bottomed flask fitted with a still-head and a well-cooled receiving flask. 107 grams of dry mercuric fluoride were then added and the reaction flask was gently heated with a free flame until reaction began.

The reaction was then allowed toproceed briskly but not too vigorously (by cooling in a bath of ice water or heating, as required) until all the ,reaction product has distilledover at about 85 C. The crude product was then steamdistilled, dried and fractionated. The main product was 1,1-difiuoro-3-bromopropane, boiling point 92 C.-94 C. Using this procedure yields of 40% of pure 1.1-difluoro-3-bromopropane are obtained. A small amount of CHzFCHzCI-IeBl' was present in the residue.

1,1,3-tribromopropane (CHBr2CHzCH2Br) likewise appears to be a new compound. It was prepared as described hereinafter.

Example AA.-Preparation of 1,1,3-

tribromopropane 22 fractionated under reduced pressure. About 600 grams of 1,1,3-tribromopropane boiling at 105 C.-107 C./30 mm. were obtained. Using the procedure just described or generally similar procedures somewhat higher and somewhat lower yields were obtained. As high as 700 grams have been obtained. Also 100-150 grams of bromoform, 20-30 grams of a low boiling liquid and varying amounts of higher boiling compounds are recovered.

The azo dye compounds of my invention can be applied to the textile materials named-hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignum sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to C.- C. and maintained at this temperature until dyeing is complete, usually one-half to two hours. From time to time throughout the dyeing operation, the material is worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

The procedure just described is applicable whether the dye compound contains a sulfato group or not. The dye compounds of the invention not containing a sulfato group are practically water-insoluble. Where a sulfato group is present, the water solubility is increased and in such cash a greater amount of the dye will go into solution.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be. for example, to 3% (by weight) of that of thetextile material although lesser or greater amounts of dye can be employed.

This application is a continuation-in-part of y copending application Serial No. 631,468, filed November 28, 1945, now U. S. Patent 2,516,302. N-difluoroalkylaminobenzene compounds are described and claimed in my copending application Serial No. 624,943. filed October 26, 1945, now U. S. Patent 2,516,107.

I claim: 1. The azo compounds having the general formula:

wherein R represents a member selected from the group consisting of a B-sulfatoethyl group, a y-sulfatopropyl group and a sulfated B/Y-dihydroxypropyl group, R1 represents a member selected from the group consisting of a 2,2-difluoroethyl group, a 2,2-difluoro-n-propyl group, a 3,3-difluoro-n-propyl group, a 3,3-difluoro-nbutyl group and a 4,4-difluoro-n-amyl group, X represents a member selected from the group consisting of a hydrogen atom, a bromine atom and a chlorine atom, Y represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a chlorine atoiua fluorine atom, a methylsulfone group and a"trifluoromethyl group and Z represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a chlorine atom, a methyl group and an ethyl group.

2. The azo compounds having the general formula:

wherein R represents a member selected from the group consisting of a p-sulfatoethyl group, a 'y-sulfatopropyl group and a sulfated pm-dihydroxypropyl group, X represents a member selected from the group consisting of a hydrogen atom, a bromine atom and a chlorine atom, Y represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a

chlorine atom, a fluorine atom, a methylsulfone group and a trifiuoromethyl group, and Z represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a chlorine atom, a methyl group and an ethyl group.

3. The azo compounds having the general formula:

4. The azo compound having the formula:

omcnr,

is B-suliatoethyl O:CHa 5. The azo compound having the formula:

omonr: n 0,- N=N- N J31 fl-sulfatoethyl 6. The azo compound having the formula:

fl-sulfatoethyl 'I. The azo compound having the formula:

CHgC FgCH (\J B-sulmtoethyl CHQCHF! JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,015,204 Thomae et a1 Sept. 24, 1935 2,118,661 Baumann May 24, 1938 2,131,894 Knight Oct. 4, 1938 2,173,054 Hitch Sept. 12, 1939 2,194,927 Daudt et al Mar. 26, 1940 2,384,734 Felix et al Sept. 11, 1945 2,432,393 Dickey et a1. Dec. 9, 1947 OTHER REFERENCES Gilman: Organic Chemistry," 2nd ed., vol. 1, 1943, pages 962, 963. 

1. THE AZO COMPOUNDS HAVING THE GENERAL FORMULA: FIGA-01 WHEREIN R REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF B-SULFATOETHYL GROUP, A Y-SULFATOPROPYL GROUP AND A SULFATED B,Y-DIHYDROXYPROPYL GROUP, R1 REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A 2,2-DIFIUOROETHYL GROUP, A 2.2-DIFLUORO-N-PROPYL GROUP, A 3.3-DIFLUORO-N-PROPYL GROUP, A 3,3-DIFLUORO-NBUTYL GROUP AND A 4,4-DIFUORO-N-AMYL GROUP, X REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, A BROMINE ATOM AND A CHLORINE ATOM, Y REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, A BROMINE ATOM, A CHLORINE ATOM, A FLUORINE SYOM, A METHYLSULFONE GROUP AND A TRIFLUOROMETHYL GROUP AND Z REPRESENTS A MEMBER-SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, A BROMINE ATOM, A CHLORINE ATOM, A METHYL GROUP AND AN ETHYL GROUP. 